US3624053A - Trifluorovinyl sulfonic acid polymers - Google Patents
Trifluorovinyl sulfonic acid polymers Download PDFInfo
- Publication number
- US3624053A US3624053A US290184A US3624053DA US3624053A US 3624053 A US3624053 A US 3624053A US 290184 A US290184 A US 290184A US 3624053D A US3624053D A US 3624053DA US 3624053 A US3624053 A US 3624053A
- Authority
- US
- United States
- Prior art keywords
- sulfonic acid
- trifluorovinyl
- ion exchange
- acid
- trifluorovinyl sulfonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- LYCAGOQDEOWYGS-UHFFFAOYSA-N 1,2,2-trifluoroethenesulfonic acid Chemical compound OS(=O)(=O)C(F)=C(F)F LYCAGOQDEOWYGS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 title claims abstract description 10
- -1 ammonium ions Chemical class 0.000 claims abstract description 13
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 14
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- QARLOMBMXGVKNV-UHFFFAOYSA-N 1,2,2-trifluoroethenesulfonyl fluoride Chemical compound FC(F)=C(F)S(F)(=O)=O QARLOMBMXGVKNV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- TXGPGHBYAPBDAG-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-4,4-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C1(F)F TXGPGHBYAPBDAG-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012070 reactive reagent Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F28/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Definitions
- X is a member of the class consisting of hydrogen. alkali [50] metals, ammonium ions and amine ions.
- the present invention relates to novel polyacids, and, more particularly, to polymers of trifluorovinyl sulfonic acid.
- the polyacids of the present invention are prepared by the hydrolysis of polymers of trifluorovinyl sulfonyl fluoride.
- the Polymerization of trifluorovinyl sulfonyl fluoride is disclosed in our US. Pat. No. 3,041,317, issued June 26, 1962.
- the preferred polyacids of the present invention are copolymers of trifluorovinyl sulfonic acid and fluoroethylenes, such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and tetrafluoroethylene.
- Particularly preferred copolymers are those of trifluorovinyl sulfonic acid and tetrafluoroethylene.
- the polytrifluorovinyl sulfonic acids are of particular utility as ion exchange resins and as acid catalysts. Although theoretically the homopolymers of trifluorovinyl sulfonic acid are the most useful in these applications because of their highest concentration of acid groups, the polyacids generally employed are copolymers of trifluorovinyl sulfonic acids with fluorinated ethylenes, and, particularly, tetrafluoroethylene, which contain from 0.5 to 50 mole percent of the trifluorovinyl sulfonic acid, since such copolymers are more readily and less expensively obtained from the polymerization of trifluorovinyl sulfonyl fluoride.
- the hydrolysis of the trifluorovinyl sulfonyl fluoride polymer to the acid is generally obtained by reacting the starting material in the presence of water with a strong base, such as an alkali metal hydroxide or an organic amine, and thereafter exchanging the resulting salt radical with a strong inorganic, acid, such as hydrochloric, nitric or sulfuric acid.
- a strong base such as an alkali metal hydroxide or an organic amine
- the trifluorovinyl sulfonic acid resins of the present invention also have utility as thermally stable plastics.
- the surprising feature of the polyacids of the present invention is their utility as acid catalysts.
- the polymeric trifluorovinyl sulfonic acids catalyze reactions normally catalyzed by sulfuric acid, such as the hydrolysis of esters, or correspondingly the manufacture of esters from alcohols and acids. since the reaction is an equilibrium reaction, the formation of acetals by the reaction of aldehydes with alcohols, and the hydrolysis of organic nitriles to carboxylic acids.
- the advantages resulting from the use of polymeric trifluorovinyl sulfonic acid as an acid catalyst are substantial.
- the polymeric trifluorovinyl sulfonic acids of the present invention are extremely temperature stable and chemically inert and, thus, do not interfere in the reaction catalyzed. They permit the use of highly corrosive or reactive reagents and, furthermore, permit the operation of the acid catalyzed reaction at extremely high temperatures.
- the great advantage of the trifluorovinyl sulfonic acid resin over sulfuric acid is the ready separation of the reaction products from the catalyst, the ability to regenerate the catalyst, the absence of sulfuric acid waste, and the noncorrosiveness of the catalyst.
- the invention is further illustrated by the following example.
- EXAMPLE Into a stainless steel shaker tube was charged 13 g. of trifluorovinyl sulfonyl fluoride, 30 ml. of perfluorodimethylcyclobutane, and g. of gaseous tetrafluoroethylene. A separate vessel of 60 ml. volume was filled with a gaseous mixture of 2.2 percent by weight of N F, in nitrogen to a pressure removed under vacuum while heating the flask with an infrared lamp. The residue of l3.5 g. of copolymer remained in the flask. The product was combined with 250 ml. of water and cut in a high-speed blender. It was isolated by filtration, air dried, and passed through a 20 mesh screen.
- the SO Na groups in the hydrolyzed product were converted to SO -,l-l groups by an ion exchange reaction carried out as follows:
- the hydrolyzed copolymer was stirred in 150 ml. of a 1:1 volumetric mixture of methanol and concentrated hydrochloric acid and heated under reflux for a period of 16 hours.
- the product was removed by filtration and washed with a 1:1 volumetric mixture of methanol and water. After vacuum drying at C. 7.6 g. of copolymer containing SO H groups was recovered.
- the trifluorovinyl sulfonic acid copolymers of the present invention can be readily converted to other monovalent metal salts or salts of other monovalent anions such as the ammonium ion or amine ions.
Abstract
1. A normally solid ion exchange resin polymer of trifluorovinyl sulfonic acid containing units of the structure
WHERE X is a member of the class consisting of hydrogen, alkali metals, ammonium ions and amine ions.
WHERE X is a member of the class consisting of hydrogen, alkali metals, ammonium ions and amine ions.
Description
O ilmted States Patent 1n13.624.053
[72] Inventors Hugh Harper Gibbs [56] References Cited w s UNITED STATES PATENTS [2 AD I No g z t' g Grimm 3,014.3 7 6/1962 Gibbs zoo/2.2
P ,l 4 Filed J 1963 3 28 298 4/l96 Lefevre 260/79 3 [45] patented No 30, 1971 Primary Examiner-Joseph L. Schofer [73] Assignee E. I. du Pont de Nemours and Company swam Hummer-C Henderwm Wllmington, Del. Al!0rney-Herbert W. Larson The portion of the term of the patent subsequem to June 1979' has been CLAIM: l. A normally solid ion exchange resin polymer of disclalmed.
' tnfluorovmyl sulfonic acid containing units of the structure [54] TRIFLUOROVINYL SULFONIC ACID POLYMERS Fade 3 Claims, No Drawings S 01X [52] US. Cl 260/793 R, W.
260/22 R, 260/793 M, 260/543 F [51 Int. Cl C08f 13/00 where X is a member of the class consisting of hydrogen. alkali [50] metals, ammonium ions and amine ions.
Field of Search 260/793 M TRIFLUOROVINYL SULFONIC ACID POLYMERS The present invention relates to novel polyacids, and, more particularly, to polymers of trifluorovinyl sulfonic acid.
The polyacids of the present invention are prepared by the hydrolysis of polymers of trifluorovinyl sulfonyl fluoride. The Polymerization of trifluorovinyl sulfonyl fluoride is disclosed in our US. Pat. No. 3,041,317, issued June 26, 1962. The preferred polyacids of the present invention are copolymers of trifluorovinyl sulfonic acid and fluoroethylenes, such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and tetrafluoroethylene. Particularly preferred copolymers are those of trifluorovinyl sulfonic acid and tetrafluoroethylene.
The polytrifluorovinyl sulfonic acids are of particular utility as ion exchange resins and as acid catalysts. Although theoretically the homopolymers of trifluorovinyl sulfonic acid are the most useful in these applications because of their highest concentration of acid groups, the polyacids generally employed are copolymers of trifluorovinyl sulfonic acids with fluorinated ethylenes, and, particularly, tetrafluoroethylene, which contain from 0.5 to 50 mole percent of the trifluorovinyl sulfonic acid, since such copolymers are more readily and less expensively obtained from the polymerization of trifluorovinyl sulfonyl fluoride.
The hydrolysis of the trifluorovinyl sulfonyl fluoride polymer to the acid is generally obtained by reacting the starting material in the presence of water with a strong base, such as an alkali metal hydroxide or an organic amine, and thereafter exchanging the resulting salt radical with a strong inorganic, acid, such as hydrochloric, nitric or sulfuric acid.
In addition to their utility as ion exchange resins and acid catalysts, the trifluorovinyl sulfonic acid resins of the present invention also have utility as thermally stable plastics.
The surprising feature of the polyacids of the present invention, however, is their utility as acid catalysts. Thus, it was found that the polymeric trifluorovinyl sulfonic acids catalyze reactions normally catalyzed by sulfuric acid, such as the hydrolysis of esters, or correspondingly the manufacture of esters from alcohols and acids. since the reaction is an equilibrium reaction, the formation of acetals by the reaction of aldehydes with alcohols, and the hydrolysis of organic nitriles to carboxylic acids. The advantages resulting from the use of polymeric trifluorovinyl sulfonic acid as an acid catalyst are substantial. Aside from the sulfonic acid group, the polymeric trifluorovinyl sulfonic acids of the present invention are extremely temperature stable and chemically inert and, thus, do not interfere in the reaction catalyzed. They permit the use of highly corrosive or reactive reagents and, furthermore, permit the operation of the acid catalyzed reaction at extremely high temperatures. The great advantage of the trifluorovinyl sulfonic acid resin over sulfuric acid is the ready separation of the reaction products from the catalyst, the ability to regenerate the catalyst, the absence of sulfuric acid waste, and the noncorrosiveness of the catalyst.
The invention is further illustrated by the following example.
EXAMPLE Into a stainless steel shaker tube was charged 13 g. of trifluorovinyl sulfonyl fluoride, 30 ml. of perfluorodimethylcyclobutane, and g. of gaseous tetrafluoroethylene. A separate vessel of 60 ml. volume was filled with a gaseous mixture of 2.2 percent by weight of N F, in nitrogen to a pressure removed under vacuum while heating the flask with an infrared lamp. The residue of l3.5 g. of copolymer remained in the flask. The product was combined with 250 ml. of water and cut in a high-speed blender. It was isolated by filtration, air dried, and passed through a 20 mesh screen. A 0.3 g. portion of the product was pressed at 275 C. to give a coherent film. The film showed a strong absorbance band at 6.85 microns in the infrared spectrum, which is evidence of incorporation of the comonomer containing SO groups.
In order to hydrolyze pendent -SO F groups in the copolymer to -SO;,Na groups, an 8.6 g. portion of the copolymer was heated for 5 hours at 150 C. in the presence of a liquid medium consisting of 4 ml. of 50 percent by weight aqueous sodium hydroxide solution, ml. of methanol and 10 ml. of triethylamine. The hydrolyzed copolymer was recovered by filtration, washed with methanol and air dried.
The SO Na groups in the hydrolyzed product were converted to SO -,l-l groups by an ion exchange reaction carried out as follows: The hydrolyzed copolymer was stirred in 150 ml. of a 1:1 volumetric mixture of methanol and concentrated hydrochloric acid and heated under reflux for a period of 16 hours. The product was removed by filtration and washed with a 1:1 volumetric mixture of methanol and water. After vacuum drying at C. 7.6 g. of copolymer containing SO H groups was recovered.
The presence of SO;,H groups was verified by titration as follows: A 0.9146 g. sample of the acid resin copolymer was combined with l g. of sodium chloride and about 20 ml. of a 1:1 volumetric mixture of methanol and water. The mixture was sparged with nitrogen, and 3 ml. of standard 0.1 N sodium hydroxide was added. The mixture was stirred for several hours, and excess sodium hydroxide was determined by back titration with standard 0.1 N hydrochloric acid to the methyl red endpoint. The sample was found to contain 0.065 milliequivalents of SO H groups, showing it to be an ion exchange resin having an equivalent weight of approximately 14,000.
Employing the foregoing procedure, it is possible to prepare trifluorovinyl sulfonic acid resins containing higher concentrations of polymerized trifluorovinyl sulfonic acid by employing higher concentrations of trifluorovinyl sulfonyl fluoride in the polymerization, including homopolymers. Vinyl fluoride, vinylidene fluoride, trifluoroethylene or chlorotrifluoroethylene can be substituted for the tetrafluoroethylene to give rise to the corresponding copolymers.
In their capacity as ion exchange resins, the trifluorovinyl sulfonic acid copolymers of the present invention can be readily converted to other monovalent metal salts or salts of other monovalent anions such as the ammonium ion or amine ions.
We claim:
1. A normally solid ion exchange resin polymer of trifluorovinyl sulfonic acid containing units of the structure where X is a member of the class consisting of hydrogen, alkali metals, ammonium ions and amine ions.
2. A normally solid ion exchange resin copolymer of a fluoroethylene and trifluorovinyl sulfonic acid containing units of the structure where X is a member of the class consisting of hydrogen, alkali metals and ammonium ions and amine ions.
3. The copolymer of claim 2 wherein the fluoroethylene is tetrafluoroethylene.
l l I I i
Claims (3)
1. A NORMALLY SOLID ION EXCHANGE RESIN POLYMER OF TRIFLUOROVINYL SULFONIC ACID CONTAINING UNITS OR THE STRUCTURE -CF2-CF(-SO2-O-X)WHERE X IS A MEMBER OF THE CLASS CONSISTING OF HYDROGEN, ALKALI METALS, AMMONIUM IONS AND AMINE IONS.
2. A normally solid ion exchange resin copolymer of a fluoroethylene and trifluorovinyl sulfonic acid containing units of the structure where X is a member of the class consisting of hydrogen, alkali metals and ammonium ions and amine ions.
3. The copolymer of claim 2 wherein the fluoroethylene is tetrafluoroethylene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29018463A | 1963-06-24 | 1963-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3624053A true US3624053A (en) | 1971-11-30 |
Family
ID=23114885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US290184A Expired - Lifetime US3624053A (en) | 1963-06-24 | 1963-06-24 | Trifluorovinyl sulfonic acid polymers |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3624053A (en) |
| GB (1) | GB1004449A (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120903A (en) * | 1977-03-30 | 1978-10-17 | E. I. Du Pont De Nemours And Company | Method for preparing poly(tetramethylene ether) glycol |
| US4139567A (en) * | 1977-03-30 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Method for preparing copolyether glycols |
| US4153786A (en) * | 1977-03-30 | 1979-05-08 | E. I. Du Pont De Nemours And Company | Method for preparing ester end-capped copolyether glycols |
| DE2917085A1 (en) * | 1978-05-10 | 1979-11-22 | Varen Technology | Oxyalkylation of hydroxy-cpds. with alkylene oxide - in the presence of a sulphonated per:fluorocarbon! polymer, giving mono:oxyalkylated deriv. selectively |
| US4180695A (en) * | 1976-03-04 | 1979-12-25 | Shell Oil Company | Isoparaffin alkylation process using an unsupported perfluorinated polymer catalyst |
| US4185142A (en) * | 1978-08-09 | 1980-01-22 | Diamond Shamrock Corporation | Oxygen electrode rejuvenation methods |
| US4188308A (en) * | 1976-02-23 | 1980-02-12 | Varen Technology | Conversion of pendant sulfonate groups to sulfonic acid groups on perfluorvinylether-tetrafluoroethylene copolymer catalysts |
| DE3020260A1 (en) * | 1979-05-29 | 1980-12-11 | Diamond Shamrock Corp | METHOD FOR PRODUCING CHROME ACID USING TWO-ROOM AND THREE-ROOM CELLS |
| DE3020261A1 (en) * | 1979-05-29 | 1980-12-11 | Diamond Shamrock Corp | METHOD AND DEVICE FOR PRODUCING CHROME ACID |
| DE3034578A1 (en) * | 1979-10-01 | 1981-04-09 | W.R. Grace & Co., 10036 New York, N.Y. | SILICONE RULE AND ELECTRODIALYSIS PROCESS FOR PRODUCING IT |
| DE3020057A1 (en) | 1979-05-31 | 1981-05-27 | Asahi Kasei Kogyo K.K., Osaka | FLUORINATED CATION EXCHANGER MEMBRANE AND METHOD FOR THE PRODUCTION THEREOF |
| US4275228A (en) * | 1978-05-17 | 1981-06-23 | Rhone-Poulenc Industries | Catalytic preparation of ethyl acetate |
| US4303551A (en) * | 1976-02-23 | 1981-12-01 | Varen Technology | Supported catalyst |
| US4317949A (en) * | 1976-02-23 | 1982-03-02 | Varen Technology | Alkylation process and apparatus useful therein |
| US4357218A (en) * | 1974-03-07 | 1982-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Cation exchange membrane and use thereof in the electrolysis of sodium chloride |
| US4409403A (en) * | 1976-02-23 | 1983-10-11 | Varen Technology | Oxyalkylation process |
| US4410404A (en) * | 1981-06-26 | 1983-10-18 | Diamond Shamrock Corporation | Membrane cell at increased caustic concentration |
| US4434116A (en) | 1981-06-26 | 1984-02-28 | Diamond Shamrock Corporation | Method for making a porous fluorinated polymer structure |
| US4460458A (en) * | 1982-07-14 | 1984-07-17 | Mobil Oil Corporation | Process for demetalizing petroleum utilizing strong solid-phase Bronsted acids |
| US4504685A (en) * | 1978-05-10 | 1985-03-12 | Varen Technology | Oxyalkylation process |
| US5105047A (en) * | 1989-08-02 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents |
| US5124299A (en) * | 1989-08-02 | 1992-06-23 | E. I. Du Pont De Nemours And Company | Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents |
| US5691066A (en) * | 1996-06-25 | 1997-11-25 | Acushnet Company | Golf ball comprising fluoropolymer and method of making same |
| US5962140A (en) * | 1996-06-25 | 1999-10-05 | Acushnet Company | Golf ball comprising fluoropolymer |
| US6468712B1 (en) | 2000-02-25 | 2002-10-22 | Massachusetts Institute Of Technology | Resist materials for 157-nm lithography |
| US20030152864A1 (en) * | 2000-04-04 | 2003-08-14 | Daikin Industries, Ltd. | Novel fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same |
| US20050004335A1 (en) * | 2003-06-11 | 2005-01-06 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Polymer electrolyte of high durability and a production process thereof |
| US20060014886A1 (en) * | 2004-07-19 | 2006-01-19 | 3M Innovative Properties Company | Method of purifying a dispersion of ionic fluoropolymer |
| WO2006038928A1 (en) * | 2004-07-19 | 2006-04-13 | 3M Innovative Properties Company | Method of hydrolyzing a dispersion of ionic fluoropolymer |
| US20060135715A1 (en) * | 2003-06-27 | 2006-06-22 | Zhen-Yu Yang | Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes |
| US20090143624A1 (en) * | 2007-11-30 | 2009-06-04 | E. I. Dupont De Nemours And Company | Compositions of and processes for producing poly(trimethylene glycol carbonate trimethylene glycol ether) diol |
| US20120107726A1 (en) * | 2009-03-30 | 2012-05-03 | Piotrek Co., Ltd. | Process for producing fluorine containing polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014317A (en) * | 1959-11-30 | 1961-12-26 | Louis J Hansen | Finishing wheel for shoe machinery |
| US3128298A (en) * | 1960-02-04 | 1964-04-07 | Dow Chemical Co | Surfactive low polymers |
-
1963
- 1963-06-24 US US290184A patent/US3624053A/en not_active Expired - Lifetime
-
1964
- 1964-06-18 GB GB25247/64A patent/GB1004449A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014317A (en) * | 1959-11-30 | 1961-12-26 | Louis J Hansen | Finishing wheel for shoe machinery |
| US3128298A (en) * | 1960-02-04 | 1964-04-07 | Dow Chemical Co | Surfactive low polymers |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4357218A (en) * | 1974-03-07 | 1982-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Cation exchange membrane and use thereof in the electrolysis of sodium chloride |
| US4409403A (en) * | 1976-02-23 | 1983-10-11 | Varen Technology | Oxyalkylation process |
| US4188308A (en) * | 1976-02-23 | 1980-02-12 | Varen Technology | Conversion of pendant sulfonate groups to sulfonic acid groups on perfluorvinylether-tetrafluoroethylene copolymer catalysts |
| US4317949A (en) * | 1976-02-23 | 1982-03-02 | Varen Technology | Alkylation process and apparatus useful therein |
| US4303551A (en) * | 1976-02-23 | 1981-12-01 | Varen Technology | Supported catalyst |
| US4180695A (en) * | 1976-03-04 | 1979-12-25 | Shell Oil Company | Isoparaffin alkylation process using an unsupported perfluorinated polymer catalyst |
| US4120903A (en) * | 1977-03-30 | 1978-10-17 | E. I. Du Pont De Nemours And Company | Method for preparing poly(tetramethylene ether) glycol |
| US4139567A (en) * | 1977-03-30 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Method for preparing copolyether glycols |
| US4153786A (en) * | 1977-03-30 | 1979-05-08 | E. I. Du Pont De Nemours And Company | Method for preparing ester end-capped copolyether glycols |
| DE2917085A1 (en) * | 1978-05-10 | 1979-11-22 | Varen Technology | Oxyalkylation of hydroxy-cpds. with alkylene oxide - in the presence of a sulphonated per:fluorocarbon! polymer, giving mono:oxyalkylated deriv. selectively |
| US4504685A (en) * | 1978-05-10 | 1985-03-12 | Varen Technology | Oxyalkylation process |
| US4275228A (en) * | 1978-05-17 | 1981-06-23 | Rhone-Poulenc Industries | Catalytic preparation of ethyl acetate |
| US4185142A (en) * | 1978-08-09 | 1980-01-22 | Diamond Shamrock Corporation | Oxygen electrode rejuvenation methods |
| DE3020261A1 (en) * | 1979-05-29 | 1980-12-11 | Diamond Shamrock Corp | METHOD AND DEVICE FOR PRODUCING CHROME ACID |
| DE3020260A1 (en) * | 1979-05-29 | 1980-12-11 | Diamond Shamrock Corp | METHOD FOR PRODUCING CHROME ACID USING TWO-ROOM AND THREE-ROOM CELLS |
| DE3020057A1 (en) | 1979-05-31 | 1981-05-27 | Asahi Kasei Kogyo K.K., Osaka | FLUORINATED CATION EXCHANGER MEMBRANE AND METHOD FOR THE PRODUCTION THEREOF |
| DE3050439A1 (en) * | 1979-05-31 | 1982-07-22 | ||
| DE3050439C2 (en) * | 1979-05-31 | 1989-11-09 | Asahi Kasei Kogyo K.K., Osaka, Jp | |
| DE3034578A1 (en) * | 1979-10-01 | 1981-04-09 | W.R. Grace & Co., 10036 New York, N.Y. | SILICONE RULE AND ELECTRODIALYSIS PROCESS FOR PRODUCING IT |
| US4410404A (en) * | 1981-06-26 | 1983-10-18 | Diamond Shamrock Corporation | Membrane cell at increased caustic concentration |
| US4434116A (en) | 1981-06-26 | 1984-02-28 | Diamond Shamrock Corporation | Method for making a porous fluorinated polymer structure |
| US4460458A (en) * | 1982-07-14 | 1984-07-17 | Mobil Oil Corporation | Process for demetalizing petroleum utilizing strong solid-phase Bronsted acids |
| US5105047A (en) * | 1989-08-02 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents |
| US5124299A (en) * | 1989-08-02 | 1992-06-23 | E. I. Du Pont De Nemours And Company | Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents |
| US5691066A (en) * | 1996-06-25 | 1997-11-25 | Acushnet Company | Golf ball comprising fluoropolymer and method of making same |
| US5962140A (en) * | 1996-06-25 | 1999-10-05 | Acushnet Company | Golf ball comprising fluoropolymer |
| US6468712B1 (en) | 2000-02-25 | 2002-10-22 | Massachusetts Institute Of Technology | Resist materials for 157-nm lithography |
| US20030152864A1 (en) * | 2000-04-04 | 2003-08-14 | Daikin Industries, Ltd. | Novel fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same |
| US20050287471A1 (en) * | 2000-04-04 | 2005-12-29 | Daikin Industries, Ltd. | Novel fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same |
| US6908724B2 (en) | 2000-04-04 | 2005-06-21 | Daikin Industries, Ltd. | Fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same |
| US20050004335A1 (en) * | 2003-06-11 | 2005-01-06 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Polymer electrolyte of high durability and a production process thereof |
| US7414102B2 (en) | 2003-06-11 | 2008-08-19 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Polymer electrolyte of high durability and a production process thereof |
| US20060135715A1 (en) * | 2003-06-27 | 2006-06-22 | Zhen-Yu Yang | Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes |
| US20060014886A1 (en) * | 2004-07-19 | 2006-01-19 | 3M Innovative Properties Company | Method of purifying a dispersion of ionic fluoropolymer |
| WO2006038928A1 (en) * | 2004-07-19 | 2006-04-13 | 3M Innovative Properties Company | Method of hydrolyzing a dispersion of ionic fluoropolymer |
| US7304101B2 (en) | 2004-07-19 | 2007-12-04 | 3M Innovative Properties Company | Method of purifying a dispersion of ionic fluoropolymer |
| US20090143624A1 (en) * | 2007-11-30 | 2009-06-04 | E. I. Dupont De Nemours And Company | Compositions of and processes for producing poly(trimethylene glycol carbonate trimethylene glycol ether) diol |
| US20120107726A1 (en) * | 2009-03-30 | 2012-05-03 | Piotrek Co., Ltd. | Process for producing fluorine containing polymer |
| US9562126B2 (en) * | 2009-03-30 | 2017-02-07 | Piotrek Co., Ltd. | Process for producing fluorine containing polymer |
| US9979037B2 (en) | 2009-03-30 | 2018-05-22 | Piotrek Co., Ltd. | Process for producing fluorine containing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1004449A (en) | 1965-09-15 |
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